Polar quikontl sclphonamides as



ma ems omen STATE roma aUmom suu'nonamoss as i ram-mm AIDS ennui Kienle are Chester Albert Amick, Brook, N. 1., assignors to American anamid Company, New York, N. Y., a corpo tionoflilaine- No 1mm. Application Julyl, 1e43,

* Serial-No.4,131

10 Claim.

This invention'relates to a new type of dyeing and printing assistant, dyecomposltions containing these assistants and products printed therefrom.

Use of printing-color pastes containing dyes,

(Cl. 8-" factlire of the paste is not only 'tion they are thus generally more uniformly dispersed throughout a printing-color paste made particularly-in printing operations using vat dyes. is'sumciently well-knownso that the procedure v become almost standardized. The actual color 'source may be. either a dye paste or a dye powder;

Iniddltion to the real color, a dyepaste usually contains agents to prevent drying-out, settling and/or Dye powders, not being subject to,v these difficulties, do not require these agents.

but they contain 88ents or are so proces'sedas to promote dispcrsibility.

.In either case, the dyepaste or dye powder must be admixed with suitable thickener, usually therefrom. As a result, the printing assistants usually operate more effectively when the printing-color pastels finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making up printing-color pastes have been available. Most of the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders, the latter being necessarily a sum dispersion, to forms printing-color paste a which is, suitable for application. In the case of vatdyes, it is also to add a reducing agent-and usually an alkali. Becausethecolor yield from printing-color pastes often decreases rapidly as the paste ages after being made up,

the'ae printing-,color pastes are usually p epared by the fabric finishers just before they are to be 7 e, printlngscolor pastes, however compounded, are then applied to textile. paper or other fabric materials .for decorative or protective purposes. The printed pieces are dried, agedin a steam ager, treatedwith' anoxidizing agent, rinsed and finally dried." Usually in'processing textiles,- printed fabric alsogis soaped at or near the "boil with about a 0.1% soap solution and a ain rinsed before the final dryinsr p ration,

In making up and applying printing-.color'pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtainin: maximum color yield. .lhe exact way in which these act to produee'an improved color yield in printing is not entirely understood. It is with these printing aids or assistants that the present invention is particularly concerned.

Although printing aids are desimble in the 'printing-eolorpastes, the exact point at which they areadded may Dye pastes may contain printing-aids as one of their components and tins-color. made therefrom obviously contain the'printing assistant. Where a printing assistant is not present in the dye paste,

.itmaybeaddedatthetimeofmakingupthe It is preferable however, that the printing assistant he I 'i'heiradditicnatthe prop rpoint inthemanumuieactuaidycpute.

limited to the use of dry solids. Nevertheless, .it is desirable that printing assistants be incorpov rated in the powders-at the time of manufacture A for the same reasons which apply in the caseof dye pastes. e I V Dye pastes containing various liquid printing assistants have been made. Among theliquid materials used are the alkylolamines', for example,"

triethanol amine; and] or polyhydric alcohols such as giycerine, glycol,diethylene glycol and the like.

Various derivatives therefrom also have been tried. Iiil a printing aid is to be incorporated in a dye powder, a solid printing aid is necessary. Examples of such solids which have been used in the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone betasulphonate); anthraquinone and certain metal salts such as those of cobalt and iron.

Unfortunately, most of these printing aids previously used are not as satisfactory as may he desired. Many of them will not in all cases produce 7 the'intensiflcation of color for which they were intended. Others, such as the polyhydric alcohols, cause deterioration of .the printing-color pastes so that marked variations in the strength of prints therefrom are observable even after the printing-color paste has been allowed to stand for only a relatively short time. Many of them are satisfactory with somecolors but have an adverse eifect on others, even-to the extent of visibly altering the shade. None of them are suitable without. 1 modification for use both in paste and powder .compositions.

There remains, therefore, a demand for suitable printing "assistant which will produce. a satis-- factory eolor intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably the assistants should be useful both with dye and dye powders and in addition should be readily available orcheaply and easily prepared. It is, therefore, the object of the present invention to pro:

easier, but in addivide a new type of printing assistant which posisolated,

sesses these desirable Prop rties.

In general the objects of the present invention are accomplished by using as a printing assistant a quinonyl-suiphonamide having a terminal polar latter with diethanolamine.

group.. Such compounds may be represented by the general formula 1 ethylene diamine and the other alkyl'ene an amines, guanidine carbonate, biguanide, melaz mine and the like. a

'in which Q represents the residue of a quinone such as alpha or beta anthraquinone and betanaphthoquinone; R1 and R2 represent hydrogen with-ethanol amine. This compound gives an excellent printing assistant. Similarly, the N-diethanol sulphonamides of beta-'anthraquinone sulphonic acid may be prepared by reacting the Other useful prodnets are obtained for example by the condensation of. a 'quinone-sulphonyl chloride and urea,

While the dye and printing paste compositions of the present invention are not limited to the use of any particular dyes or dye forms; they are especially suitable for use with vat-dyes in either n alkanol, aminoethyl, c y a 00 15' paste or powder form. Particularly good results densed carbanryl radical and 'a: may be 1 or 2.- Typical of the sulphonamides containing additional polar groups suitable for use according to the present invention are the monoand which may be represented by the formulae:

So far as the present invention is concerned the assistants may be added to the printing-color pastes at any point. They may be incorporated may be obtained using the-vat-dyev powders of high autodispersibility set forth in Crossley et 8.1., United States Reissue Patent 21,402, reissued March 19', 1940. By combining the color matedi-N-ethanol,beta-anthraquinonylsulphonamides go rials or that atent into printingaste'compositions containing the printing assistants of the present "invention, the full. advantages of both may be gained with a resultant simplicity in use and excellence of shade and sharpness of color.

The invention will be more fully-set forth in connection with the following examples which are intended to be illustrative and not by way of limitation. All parts are by weight unless other- .wisenoted.

In the succeeding examp1es,-test prints were cotton print-cloth. Ageing of the prints was carried out in a steam ager which was constructed in such a manner that controlled temperatures could'be used. The temperature range normally used was 100-l05 C. Those ageings referred to the thickener; into the dye pastes or 40 as plant or hot ageings were carried out in the ders or may be blended directly into the printingcolor paste. However, as pointed out above, it is preferable that they be incorporated in the dye paste or powder during manufacture.

temperature range of about 106-110 C.- In the case of the cotton prints ageing periods of 3 minutes, 5 minutes or both were used. 0n rayon, ageing periods of 5 and 10 minutes or both were The use of this new class 0! printing assistants used. The shortest period which gives a satisfacpossesses a number of important advantages. These compounds are dry solids, which may be readily powdered and blended in dye powders but are also soluble or dispersible in dye paste suscation in both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields even under hot ageing contory ag'eing is preferable.

Example 1 I Apaste was prepared by slurrying 2,000 parts p sio s- T y fiv ,.therefore, a general appliso of British gum (Stein Hall) in 5,000 parts of water and the mixture was heated with contin-' uous' stirring until the temperature reached about 185 1. Heating was continued for about 1% hours after which 450 parts of powdered sodium ditions. Their useis simple since they may be carbonate and 450 parts of powde ed Potassium employed as powders, as suspensions in water or are impractical to form.v

Compounds such as those used according to the present invention are readily prepared by-con- 7o dcnsing a quinone-suiphonic acid with orby reacting. a quinone-sulphonyl chloride with a suit able I'br example, the N-ethanol betaanthraquinone sulfonamide may be prepared by reacting beta-anthraquinone sulphonyl chloride tinued until the temperaturedecreased to beta-naphthoquinone.

carbonate were added and the mixture stirred until the carbonates dissolved] Heating was discontinued but stirring continued until the temperature reached approximately F. at which time 700 parts of sodium suiphoxylate formaldehyde were dissolved therein, 600 parts of glycerine. were-added and the paste bulked to about 10,000 parts with water. Stirring was continued until the paste cooled to room temperature. In

y' A in 0856 Q 5 the succeeding examples this paste is referred to thoquinone, a: in the generic formula is ordinarily one since the disulphonamides of naphthoquinone as thickener A. a Example 2 120 parts of 3-2 British gum (Stein Hall) and sulphonamide. To this was added 97.25 parts of aldehyde were F. .at' which time 1,200 parts or potassium carhonate which had been previously dissolved in 1,000 parts oi water was added to the cooked gum 1,560 parts or sodium sulphoxylate tormdissolved in 1,500 parts of water at a temperature of about 140 F. and added to the common mixture with stirring until the whole was thoroughly mixed. 360 parts of giycerine were added and after thorough stirring the whole was bulked to about 12,000 parts. in the succeeding examples this is referred to, as thick-;

ener B.

- Example 3 2.5 grams of dispersible Golden Orange (3- powder (C. I.- 1096), prepared according to United States Reissue Patent No. 21,402 and containing approximately 0.5 part of real color, were blended with 0. 25 part of N-ethanol beta-anthraquinonethickener'B, and the whole thoroughly mixed to produce a printing-color paste, A duplicate sam ple of the above was prepared except that no printing assistant was added and the amount of thickener B was 97.5 parts. Both pastes were printed on samples of cotton. The printed pieces were dried in a hot air oven, aged, oxidized,- soaped at the boil for five minutes with a 0.1%

soap solution, rinsed and finally iron dry. Definitely better prints were obtained from the pas containing the printing assistant.

Example4 The procedure of Example 3 was repeated ex-.

actly except that the Golden Orange G .was replaced by Dark Blue B0 powder (C. I.-1099). Prints obtained from the pastes containing the printing assistant were definitely stronger and 1 superior to the prints that were made from the paste which contained no assistant.

Example 5 The procedure of Example 3 was repeated except that the, condensation product obtained from alpha-anthraquinone-sulphonic acid and monoethanolaniine was used in place of the betaanthraquinone derivative. Prints obtained fromv the pastes containing the printing assistant were definitely superior to those obtained i'rom the paste which had no printing assistant present.

Egggmple 6 The procedure of"" fiample 5 was repeated except that the Dark Blue powder or Example 4 was Prints obtained from the paste in which the printing as t was present were definitely superior to the color value of the. prints obtained from the paste in which no printing assistant was used.

' Example 7 .A sample of. wet presscake ot Vat Orange R (C. Ir-1217) was dispersedwith a sodium salt of disul hophthylmethane. Alter adjusting the ure with water to contain 13% realcolor, lo parts of the mass was with 0.5 part of N-ethanol beta-anthraquinonesulphonr amide. To thiswas added 89.5 parts of thickener B. A second paste was pron red by mixing together 10 parts of the Vet Orange R and 90 parts of thickener B. This was the control sample. Both pastes were printed on samples oi rayon and cotton. The printed pieces were dried in a hot airoven, aged ina steam'ager, oxidised.

rinsed, soaped at the boil, (or live in a 70 printing assistaii Example 9 The procedure of Example 7 was repeated except that N-ethanol alpha-anthraquinone-sulphonamide was used. Again, improved printing was obtained when used.

Emniple 10 the condensation product of beta-naphthoquinone sulphonic acid and ethanolamine as a. printing assistant. -As in Example 7, noticeably brighter and clearer prints were obtained when the condensation product was present in the printin Paste.

' Ezample'1i The procedure of Example 7 was repeated exactly' except that N-(beta-aminoethyi) beta-anthraquinonesulphonamide was used as the printing assistant. ,Prints obtained from the paste containing the printingassistant were definitely brighter and stronger than the prints obtained from the paste with water only. Example 1i.

actly except that the reaction product of betaanthraquiiione-sulphonic acid and urea was used in place of the N-ethano1 beta-anthraquinonesulphcnamide. The color values of the prints which were obtained from the-paste in' which the t was present were definit ly superior than the color values of the prints ob.- tained rrom the pastein which no Printing as- Y sistant was used. This was particularly notice- The procedure of Example Twas repeated exthe printing assistant was The procedure of Example I was followed using able when ageings were made under practical mill conditions..

-' Example 13 procedure .0! Example? waslfoilowed except that the condensation product of betaanthraquinone-sulphonic acid and melamine was 'used as the printing assistant. ,The prints dbtained from the Dastein which the printing assistant was used were stronger and brighter than the prints obtained ing thickener only.

iz'rum lcu Iv actl except that printing thickener A was used 7 in place or printing thickener B. Prints'made from the paste'eontaining'the printing assistant and thickener A were definitely superior' to those prints made from the paste containin no print-- ing'" assistant. v Example-'16 from the paste contain- V The procedure oilixample'l was repeated ex- (c. 1.-.11-1a prepared swam States Reissue Patentlio. 21,402 and containing approximately 1 part of real dye were blended with 0.3 port of N-ethanol beta-anthraquinonesuiphonamide. Tothismixturewasaddedmpartsofthickener B, and the whole was thoroughlymixed. A second 5 parts of the Vat Yellow (30 powder were mixed with 90 parts of thickener B.

This was used as a control sample. Both pastes were printed on samples of rayon and cotton and finished in the usual manner. Prints obtained from the paste in which the printing assistant was present were definitely superior in color value to thoseobtained from the pastes in which no printing assistant was used.

We claim: o

1. A color composition comprising a vat dye and a quinone sulphonamide derivative having the general formula metric) in which represents apquinonyl radical selectedfrom the group consisting of the alphaand betaanthraquinonyl and beta-naphthaquinonyl radicals; R1 represents a radical selected from the group consisting oi hydrogen and the alkyl'ol, aminoalkyl, carbamyl and condensed carbamyl rfiicals, Rs'represents a radical-selected from the group consisting of the alhlol and amino selected from the group consisting of 1 and 2.

2. A dye powder composition comprising a vat dye and a powdered quinone sulphonamide derivative having the general formula tiles in which Q represents a quinonyl radical-selected from the group consisting of the alphaand'beta v anthraquinonyl and beta-naphthaquinonyl radicals, R1 represents a radical selected from the group consisting of hydrogen 'and the alhlol chm I i \B- .r

alkyl radicals and :r is a small whole number in which Qrepresents a quinonyl radical w from thegroup consisting of the alphaand betaanthraquinonyl and heta-naphthaquinonyl radicals, R1 represents a radical selected from the group consisting of hydrogen and the alhlol,

amino alhl, carhamyl and condensed carbamyl radicals, R: represents a radical selected from the group consisting of the alhlol and amino lalkyi radicals and: is a small whole number selected from the group consistingof i and 2.

4. A color composition according-toclaim 1 in represents the beta-naphthoquinonyl i a thickener and a quinone derivative having the general formula in which Q represents a quinonyl radicalselected from the group of the alphaand betaanthraquinonyl and beta-naphthaquinonyl radicals, R1 represents a radical selected from the roup consisting of hydrogen and the alkylol, amino alkyl, carbamyl and condensed carbamyl radicals, Rs represents a radical'selected from the group of the alkyibl and amino alkyl radicals and a: is'a small whole number selected from the group consisting of 1 and 2.

"1. Ant dye composition comprising a dye, a thickener and a quinone sulphonamide derivative having the general formula in which 9 represents a quinonyl radical selected from the group consisting of the alphaand betaanthraquinonyl and beta-naphthaquinonyl radicals, R1 represents a radical selected from the group consisting of hydrogen and the alkylol, amino alkyl, carbamyl and condensed carbamyl radicals, R2 represents a radical selected from the.

roup consisting of the alkylol and amino alkyl radicals and a: is a small whole number selected from the group consisting of 1 and 2.

8. A printing paste composition comprisinga highly-dispersed vat dye, a thickener and a quinone sulphonamide derivative having the general formula in which Q represents a quinonyl radical selected from the group consisting of the alphaand betaanthraquinonyl and beta-naphthaquinonyl radicals, R1 represents a radical selected from the group consisting of hydrogen and the alkylol,

amino alkyl, carbamyl and condensed carbamyl radicals,- R2 represents a radical selected from the group consisting of the alkylol'and amino alkyl radicals and a: is a small whole,'number selected from the group consisting of 1 and 2, obtainable by compounding a colloidized vat dye powder of high autodispersibility and the quinone sulphonamide derivative with the thickener.

9. A method of printing with cat colors which comprises printing a fabric with a printing paste composition comprising a vat dye, a thickener and 'a' quinone sulphonamide derivative having the general formula from thegroup consistingof the alphaand beta anthraquinonyl and beta-naphthaquinonyl radi cals, R1 represents a radical selected from the 51 A color composition according to claim 1 in which Q represents an anthraquinonyl group.

a 6, 'A printing pastecompcsition comprising a 78' groupconsistingof hydrogen and the alkylol, amino alk'yl, carbamyl and condensed carbamyl radicals. It; represents a radical selected from the group consisting of the alkylol and amino 'alkyl radicals and a: is a small whole number selectedirom the group consisting of 1 and 2.

man article or manufacture-comprising a in"which Q represents a quinonyl radical selected in which Q represents a quinonyl radical selected from the roup consisting of the alphaand betaanthraquinonyl' and beta-naphthaquinonyl radi cals, R1 represents a radical selected'from the roup consisting of hydrogen and the alkylol. amino alkyl, carbamyl and condensed carbamyl radicals, Ra represents a radical selected from the group consisting of the alkylol and amino alkyi radicals and .1: is a small whole number selected from the group consisting of 1 and 2. 

